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| United States Patent |
6,255,273
|
|
Musso
, et al.
|
July 3, 2001
|
Hydrofluoropolyether-based azeotropic or near azeotropic compositions
Abstract
Azeotropic or near azeotropic compositions based on
difluoromethoxy-bis(difluoromethyl ether) and/or
1-difluoromethoxy-1,1,2,2-tetrafluoroethyl difluoromethyl ether.
| Inventors:
|
Musso; Ezio (Alessandria, IT);
Basile; Giampiero (Alessandria, IT);
Girolomoni; Sauro (Alessandria, IT)
|
| Assignee:
|
Ausimont S.p.A. (Milan, IT)
|
| Appl. No.:
|
374871 |
| Filed:
|
August 16, 1999 |
Foreign Application Priority Data
| Aug 19, 1998[IT] | MI98A1904 |
| Current U.S. Class: |
510/411; 134/2; 510/175; 510/177; 510/408; 510/412; 510/415 |
| Intern'l Class: |
C11D 007/50; C23G 005/028; C23G 005/032 |
| Field of Search: |
510/405,407,408,411,412,415,175,177
134/2
|
References Cited
| Foreign Patent Documents |
| 0 695 775 A1 | Feb., 1996 | EP.
| |
| 0 805 199 A2 | Nov., 1997 | EP.
| |
| 0979839A2 | Jul., 1999 | IT.
| |
| 0980890A1 | Jul., 1999 | IT.
| |
| 0980910A2 | Feb., 2000 | IT.
| |
| WO99/63043 | Dec., 1999 | WO.
| |
Primary Examiner: Gupta; Yogendra N.
Assistant Examiner: Webb; Gregory E.
Attorney, Agent or Firm: Arent Fox Kintner Plotkin & Kahn PLLC
Claims
What is claimed is:
1. Azeotropic or near azeotropic compositions, based on
difluoromethoxybis(difluoromethyl ether) and/or
1-difluoromethoxy-1,1,2,2-tetrafluoroethyl difluoromethyl ether, selected
from the group consisting of:
composition
% by weight
I) difluoromethoxy 2-60
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1-dichloro-2,2,2-trifluoroethane 98-40
(CHCl.sub.2 CF.sub.3,HCFC 123
II) difluoromethoxy 1-95
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
n-pentane 99-5
III) difluoromethoxy 1-95
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
iso-pentane 99-1
IV) difluoromethoxy 1-60
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
dimethyl ketone (acetone) 99-40
V) difluoromethoxy 1-99
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,3,3-pentafluorobutane 99-1
(CF.sub.3 CH.sub.2 CF.sub.2 CH.sub.3, HFC 365 mfc)
VI) difluoromethoxy 1-40
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,4,4,4-hexafluorobutane 99-60
(CF.sub.3 CH.sub.2 CH.sub.2 CF.sub.3, HFC 356 ffa)
VII) difluoromethoxy 1-96
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
methoxymethyl methylether 99-14
VIII) difluoromethoxy 30-99
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
n-hexane 70-1
IX) difluoromethoxy 1-99
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
trans 1,2-dichloroethylene 99-1
(ClCHCHCl, tDCE)
X) 1-difluoromethoxy 1-93
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
n-pentane 99-7
XI) 1-difluoromethoxy 30-99
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
dimethyl ketone (acetone) 70-1
XII) 1-difluoromethoxy 50-99
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
methyl alcohol 50-1
XIII) 1-difluoromethoxy 15-99
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
n-hexane 85-1
XIV) 1-difluoromethoxy 1-99
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
trans 1,2-dichloroethylene 99-1
(ClCHCHCl)
XV) 1-difluoromethoxy 5-99
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
ethyl alcohol 95-1
XVI) difluoromethoxy- 1-42
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1-dichloro-2,2,2-trifluoroethane 98-24
(CHCl.sub.2 CF.sub.3, HCFC 123)
hydrocarbon 1-35
XVII) difluoromethoxy- 1-64
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,3,3-pentafluorobutane 98-1
(CF.sub.3 CH.sub.2 CF.sub.2 CH.sub.3, HFC 365 mfc)
hydrocarbon 1-35
XVIII) difluoromethoxy- 1-22
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,4,4,4-hexafluorobutane 98-43
(Cf.sub.3 CH.sub.2 CH.sub.2 CF.sub.3, HFC 356 ffa)
hydrocarbon 1-35
XIX) difluoromethoxy- 1-55
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1-dichloro-2,2,2-trifluoroethane 98-35
(CHCl.sub.2 CF.sub.3, HCFC 123)
alcohol 1-10
XX) difluoromethoxy- 1-89
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,3,3-pentafluorobutane 98-1
(CF.sub.3 CH.sub.2 CF.sub.2 CH.sub.3, HFC 365 mfc)
alcohol 1-10; and
XXI) difluoromethoxy- 1-35
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,4,4,4-hexafluorobutane 98-55
(Cf.sub.3 CH.sub.2 CH.sub.2 CF.sub.3, HFC 356 ffa)
alcohol 1-10.
2. Azeotropic or near azeotropic compositions according to claim 1,
selected from the group consisting of:
composition
% by weight
I) difluoromethoxy 2-54
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1-dichloro-2,2,2-trifluoroethane 98-46
(CHCl.sub.2 CF.sub.3, HCFC 123)
II) difluoromethoxy 25-95
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
n-pentane 75-5
III) difluoromethoxy 25-98
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
iso-pentane 75-2
IV) difluoromethoxy 20-60
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
ketone (acetone) 80-40
V) difluoromethoxy 10-98
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,3,3-pentafluorobutane 90-2
(CF.sub.3 CH.sub.2 CF.sub.2 CH.sub.3, HFC 365 mfc)
VI) difluoromethoxy 10-40
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,4,4,4-hexafluorobutane 90-60
(CF.sub.3 CH.sub.2 CH.sub.2 CF.sub.3, HFC 356 ffa)
VII) difluoromethoxy 25-96
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
methoxymethyl methylether 75-14
VIII) difluoromethoxy 35-98
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
n-hexane 65-2
IX) difluoromethoxy 18-95
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
trans 1,2-dichloroethylene 82-5
(ClCHCHCl, tDCE)
X) 1-difluoromethoxy 25-93
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
n-pentane 75-7
XI) 1-difluoromethoxy 50-98
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
diethel ketone (acetone) 50-2
XII) 1-difluoromethoxy 60-98
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
methyl alcohol 40-2
XIII) 1-difluoromethoxy 25-98
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
n-hexane 75-2
XIV) 1-difluoromethoxy 15-95
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
trans 1,2-dichloroethylene 85-5
(ClCHCHCl); and
XV) 1-difluoromethoxy 10-98
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
ethyl alcohol 90-2.
3. Azeotropic compositions according to claim 1 for which an absolute
minimum or maximum in the boiling temperature at the pressure of 1.013 bar
with respect to the pure products is exhibited and defined as follows:
A) difluoromethoxy- 24% by wt.
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1-dichloro-2,2,2-trifluoroethane 76% by wt.
(CHCl.sub.2 CF.sub.3, HCFC 123)
B) difluoromethoxy- 62% by wt.
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
n-pentane 38% by wt.
C) difluoromethoxy- 63% by wt.
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
iso-pentane 36% by wt.
D) difluoromethoxy- 42% by wt.
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
dimethyl ketone (acetone) 58% by wt.
E) difluoromethoxy- 60% by wt.
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,3,3-pentafluorobutane 40% by wt.
(CF.sub.3 CH.sub.2 CF.sub.2 CH.sub.3, HFC 365 mfc)
F) difluoromethoxy- 20% by wt.
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,4,4,4-hexafluorobutane 80% by wt.
(CF.sub.3 CH.sub.2 CH.sub.2 CF.sub.3, HFC 356 ffa)
G) difluoromethoxy- 59% by wt.
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
methoxymethyl methyl ether 41% by wt.
H) difluoromethoxy-
bis(difluoromethyl ether) 75% by wt.
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
n-hexane 25% by wt.
I) difluoromethoxy- 75% by wt.
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
trans 1,2-dichloroethylene 25% by wt.
(ClCHCHCl, tDCE)
1-difluoromethoxy- 61% by wt.
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
n-pentane 39% by wt.
M 1-difluoromethoxy- 79% by wt.
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
dimethyl ketone (acetone) 21% by wt.
N) 1-difluoromethoxy- 94% by wt.
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
methyl alcohol 6% by wt.
O) 1-difluoromethoxy- 74% by wt.
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
n-hexane 26% by wt.
P) 1-difluoromethoxy- 50% by wt.
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
trans 1,2-dichloroethylene 50% by wt.
(ClCHCHCl, tDCE); and
Q) 1-difluoromethoxy 95% by wt.
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
ethyl alcohol 5% by wt.
4. Near azeotropic compositions according to claim 1, selected from the
group consisting of:
composition
% by weight
I) difluoromethoxy 2-60
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1-dichloro-2,2,2-trifluoroethane 98-40
(CHCl.sub.2 CF.sub.3, HCFC 123)
III) difluoromethoxy 1-99
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
iso-pentane 99-1
IV) difluoromethoxy 1-60
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
dimethyl ketone (acetone) 99-40
V) difluoromethoxy 1-99
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,3,3-pentafluorobutane 99-1
(CF.sub.3 CH.sub.2 CF.sub.2 CH.sub.3, HFC 365 mfc)
VI) difluoromethoxy 1-40
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,4,4,4-hexafluorobutane 99-60
(CF.sub.3 CH.sub.2 CH.sub.2 CF.sub.3, HFC 356 ffa); and
VII) difluoromethoxy 1-96
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
methoxymethyl ether 99-14
wherein the difluoromethoxy-bis(difluoromethyl ether) part contains up to
40% by weight of 1-difluoromethoxyl1,1,2,2-tetrafluoroethyldifluoromethyl
ether.
5. Near azeotropic compositions according to claim 1, selected from the
group consisting of:
composition
% by weight
XI) 1-difluoromethoxy 30-99
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
dimethyl ketone (acetone) 70-1
XII) 1-difluoromethoxy 50-99
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
methyl alcohol 50-1; and
XV) 1-difluoromethoxy 5-99
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
ethyl alcohol 95-1
wherein 1-difluoromethoxy-1,1,2,2-tetrafluoroethyl difluoromethyl ether
contains up to 40% by weight of difluoromethoxy-bis(difluoromethyl ether).
6. Near azeotropic compositions according to claim 1, selected from the
group consisting of:
composition
% by weight
II) difluoromethoxy 1-95
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
n-pentane 99-5
VIII) difluoromethoxy 30-99
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
n-hexane 70-1; and
IX) difluoromethoxy 1-99
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
trans 1,2-dichloroethylene 99-1
(ClCHCHCl, tDCE)
wherein difluoromethoxy-bis(difluoromethyl ether) contains up to 50% of
1-difluoromethoxy-1,1,2,2-tetrafluoroethyl difluoromethyl ether.
7. Near azeotropic compositions according to claim 1, selected from the
group consisting of:
composition
% by weight
X) 1-difluoromethoxy 1-93
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
n-pentane 99-7
XIII) 1-difluoromethoxy 15-99
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
n-hexane 85-1; and
XIV) 1-difluoromethoxy 1-99
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
trans 1,2-dichloroethylene 99-1
(ClCHCHCl)
wherein the 1-difluoromethoxy-1,2,2,2-tetrafluoroethyl difluoromethyl ether
contains up to 50% by weight of difluoromethoxy-bis(difluoromethyl ether).
8. Near azeotropic compositions according to claim 1, based on
difluoromethoxy-bis(difluoromethyl ether) and hydrocarbons selected from
the group consisting of:
composition
% by weight
XVI) difluoromethoxy- 1-42
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1-dichloro-2,2,2-trifluoroethane 98-24
(CHCl.sub.2 CF.sub.3, HCFC 123)
hydrocarbon 1-35
XVII) difluoromethoxy- 1-64
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,3,3-pentafluorobutane 98-1
(CF.sub.3 CH.sub.2 CF.sub.2 CH.sub.3, HFC 365 mfc)
hydrocarbon 1-35; and
XVIII) difluoromethoxy- 1-22
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,4,4,4-hexafluorobutane 98-43
(CF.sub.3 CH.sub.2 CH.sub.2 CF.sub.3, HFC 356 ffa)
hydrocarbon .sup. 1-35. --
9. Compositions according to claim 8, wherein hydrocarbon is selected
between n-pentane and iso-pentane.
10. Compositions according to claim 8, wherein hydrocarbon is present in
the range 1-20% by weight.
11. Near azeotropic compositions according to claim 1, based on
difluoromethoxy-bis(difluoromethyl ether) and alcohol selected from the
group essentially consisting of:
composition
% by weight
XIX) difluoromethoxy- 1-55
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1-dichloro-2,2,2-trifluoroethane 98-35
(CHCl.sub.2 CF.sub.3, HCFC 123)
alcohol 1-10
XX) difluoromethoxy- 1-89
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,3,3-pentafluorobutane 98-1
(CF.sub.3 CH.sub.2 CF.sub.2 CH.sub.3, HFC 365 mfc)
alcohol 1-10; and
XXI) difluoromethoxy- 1-35
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,4,4,4-hexafluorobutane 98-55
(CF.sub.3 CH.sub.2 CH.sub.2 CF.sub.3, HFC 356 ffa)
alcohol .sup. 1-10. --
12. Compositions according to claim 11, wherein alcohol is methyl alcohol.
13. Compositions according to claim 11, wherein alcohol is present between
1 and 5% by weight.
14. Azeotropic or near azeotropic compositions according to claim 1,
wherein the ether part can contain at least up to 10% by weight of
hydrofluoro ethers having same structure having a boiling point in the
range 5-80.degree. C.
15. A method for removing contaminants from surfaces wherein said surfaces
are contacted with substitutes for CFC 113, comprising azeotropic and near
azeotropic compositions selected from the group consisting of:
composition
% by weight
I) difluoromethoxy 2-60
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1-dichloro-2,2,2-trifluoroethane 98-40
(CHCl.sub.2 CF.sub.3, HCFC 123)
II) difluoromethoxy 1-95
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
n-pentane 95-5
III) difluoromethoxy 1-99
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
iso-pentane 99-1
IV) difluoromethoxy 1-60
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
dimethyl ketone (acetone) 99-40
V) difluoromethoxy 1-99
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,3,3-pentafluorobutane 99-1
(CF.sub.3 CH.sub.2 CF.sub.2 CH.sub.3, HFC 365 mfc)
VI) difluoromethoxy 1-40
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,4,4,4-hexafluorobutane 99-60
(CF.sub.3 CH.sub.2 CF.sub.2 CF.sub.3, HFC 356 ffa)
VII) difluoromethoxy 1-96
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
methoxymethyl methylether 99-14
VIII) difluoromethoxy 30-99
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
n-hexane 70-1
IX) difluoromethoxy 1-99
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
trans 1,2-dichloroethylene 99-1
(ClCHCHCl, tDCE)
X) 1-difluoromethoxy 1-93
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
n-pentane 99-7
XI) 1-difluoromethoxy 30-99
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
dimethyl ketone (acetone) 70-1
XII) 1-difluoromethoxy 50-99
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
methyl alcohol 50-1
XIII) 1-difluoromethoxy 15-99
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
n-hexane 85-1
XIV) 1-difluoromethoxy 1-99
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
trans 1,2-dichloroethylene 99-1
(ClCHCHCl)
XV) 1-difluoromethoxy 5-99
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
ethyl alcohol 95-1
XVI) difluoromethoxy- 1-42
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1-dichloro-2,2,2-trifluoroethane 98-1
(CHCl.sub.2 CF.sub.3, HFC 123)
hydrocarbon 1-35
XVII) difluoromethoxy- 1-64
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,3,3-pentafluorobutane 98-1
(CF.sub.3 CH.sub.2 CF.sub.2 CH.sub.3, HFC 365 mfc)
hydrocarbon 1-35
XVIII) difluoromethoxy- 1-22
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,4,4,4-hexafluorobutane 98-43
(CF.sub.3 CH.sub.2 CH.sub.2 CF.sub.3, HFC 356 ffa)
hydrocarbon 1-35
XIX) difluoromethoxy- 1-55
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1-dichloro-2,2,2-trifluoroethane 98-35
(CHCl.sub.2 CF.sub.3, HFC 123)
alcohol 1-10
XX) difluoromethoxy- 1-89
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,3,3-pentafluorobutane 98-1
(CF.sub.3 CH.sub.2 CF.sub.2 CH.sub.3, HFC 365 mfc)
alcohol 1-10; and
XXI) difluoromethoxy- 1-35
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,4,4,4-hexafluorobutane 98-55
(CF.sub.3 CH.sub.2 CH.sub.2 CF.sub.3, HFC 356 ffa)
alcohol 1-10.
16. The method according to claim 15, wherein the compositions further
comprise one or more non-ionic surfactants wherein the concentration of
said one or more surfactants is in the range 0.005-5% by weight based on
the azeotropic or near azeotropic components.
17. The method according to claim 15, wherein the composition further
comprises solvent/drying agents.
18. The method according to claim 17, wherein stabilizers for radicalic
decomposition reactions are added to the composition in concentrations in
the range 0.1-5% by weight with respect to the solvent-detergent and/or
drying agent.
19. The method according to claim 15, wherein the compositions are combined
with one or more propellants for the cleaning electronic components.
20. The method according to claim 19, wherein the propellant is selected
from: HFC 134a (1,1,1,2-tetrafluoroethane), HFC 227ea
(1,1,1,2,3,3,3-heptafluoropropane) or mixtures thereof.
Description
The present invention relates to azeotropic or near azeotropic compositions
based on hydrofluoropolyethers (HFPE) to be used as substitutes of
1,1,2-trichloro-1,2,2-trifluoroethane (CFC 113) as a solvent.
More specifically the present invention relates to azeotropic or near
azeotropic mixtures characterized by ODP (ozone Depletion Potential)
values equal to zero or lower than 0.02, by low GWP (Global Warming
Potential) and VOC (Volatile Organic Compounds) values to be used as
detergents, i.e. as solvent for cleaning and drying agents in substitution
of CFC 113.
As it is known, CFC 113 has been widely used as solvent and/or drying agent
for industrial applications requiring the removal of organic substances
(greases, waxes, oils, resins) and/or water from solid surfaces of various
nature (metal, glass, plastics or composites surfaces).
For example, CFC 113 has been commonly used for the degreasing and removal
of abrasives from metal surfaces of mechanical parts having complex
shapes, for the cleaning of high quality and high precision metallic
components for which an accurate surface cleaning is required and for the
removal of water traces from valuable articles and from high quality
components previously subjected to washing with aqueous mediums.
Specifically in the electronic field CFC 113 has been used for the removal
of organic products and moisture traces present on the surface of molded
circuits characterized by an high density of hardly washable components
and for which an high reliability is required.
Contaminant removal processes from solid surfaces (metals, plastic
materials, glass) are carried out by methods implying the solvent action
in liquid phase (cold or hot) and/or by vapour action; in the latter case
the article is exposed to the fluid vapours at its boiling temperatures.
Vapours, by condensing on the article cold surface perform the solvent and
cleaning action.
In these applications CFC 113 has often been used also in combination with
organic solvents, in particular as azeotropic or near azeotropic mixtures
in order to substantially have the same composition in the vapour and in
the liquid phase and to avoid fractionations during the application phases
in industrial cleaning processes, during the handling, distillation and
recovery steps of the exhausted solvent.
CFC 113 is characterized by particular chemical-physical properties such as
to be advantageously used in the previously described field and allows,
furthermore, a simple, cheap and safe use since it is stable, non
flammable and non toxic.
CFCs and specifically CFC 113 have, however, the drawback to involve an
high destroying power on the stratospheric ozone layer, wherefore, the
production and commercialization have been subjected to regulations and
then banned since Jan. 1, 1995.
The need was felt to identify substitutes able to replace CFC 113 in the
mentioned use fields while respecting and protecting the environment.
To this purpose, in the solvency field, the use of alternative systems
based on aqueous solutions, of non halogenated organic solvents and of
hydrohalogenated solvents of HCFC type has been proposed.
The alternatives using the aqueous system imply however various
inconveniences.
In particular it happens that articles with microhollow, capillary holes
and surface irregularities, are insufficiently washed due to the
relatively high water surface pressure, also in the presence of
surfactants.
The water removal rate is very low and if this is not completely removed,
it can be the cause of corrosion phenomena of the metal articles
previously subjected to washing. Therefore such surfaces must be suitably
dried after they have been cleansed.
Hydrocarbons, alcohols or other non halogenated organic solvents, due to
their high flammability, have not a generalized use and require in any
case great investments in order to avoid fire and explosion risks in the
plants using them.
Furthermore, these solvents represent an atmospheric pollution source,
since, if exposed to the sun light in the presence of nitrogen oxides,
undergo oxidative degradation phenomena, with the formation of the so
called ozone-rich oxidizing smog. For this negative characteristic these
products are classified as VOC (Volatile Organic Compound) compounds.
The hydrohalogenated solvents represent a class of products more similar to
CFC 113, they give lower use complications and allow more generalized
applications in comparison with the above mentioned alternative systems.
HCFC 141b, which is one of the most valid substitutes for these
applications, has however the disadvantage to be moderately flammable and
especially to be characterized by an ODP value equal to 0.11 (CFC 11 has
ODP=l) and therefore it has been subjected to limitations.
The use of non toxic solvents having a low environmental impact,
constituted by hydrofluoropolyethers and compositions thereof having
limited concentrations of polar substances selected from alcohols, ketones
and ethers as described in the European patent application EP 805,199 is
known in the field of oil, grease, wax etc., removal from surfaces.
In said application no reference is made to mixtures having azeotropic or
near azeotropic behaviour to be used in the industrial solvency field.
In connection with what described in the prior art the need was felt to
have available substitutes to CFC 113.
It was indeed necessary to have available products able to remove oily
substances similarly to CFC 113, i.e. by partial or total solubilization
of the substances to be removed, therefore differently from pure or
additivated hydrofluoropolyethers, in order to guarantee a more accurate
and quicker cleaning of articles having complex shapes and microhollows,
with remarkable advantages in efficiency and economic saving terms of the
same cleaning operation.
Preferably the substitutes of CFC 113 should be drop-in, i.e. the
substitutes should be used in the existing plants without involving
substantial modifications and allow to maintain practically unchanged the
various operating steps of the article cleaning process.
Finally, the need was evident to limit or eliminate the environmental and
safety problems typical of the conventional solvents (hydrocarbons, HCFC),
and to reduce the cleaning operation costs deriving from the pure or only
addivitated HFPE use, since, as known, these products are obtained by
complex and expensive processes.
The Applicant has surprisingly and unexpectedly found that as substitutes
of CFC 113 hydrofluoropolyether-based (HFPE) mixtures, object of the
present invention, have azeotropic or near azeotropic behaviour, they are
drop-in of CFC 113, have an environmental impact expressed in ODP terms
equal to zero or <0.02 and low GWP and VOC values.
It is therefore an object of the present invention azeotropic or near
azeotropic compositions, based on difluoromethoxy-bis(difluoromethyl
ether) (HFPE1) and on 1-difluoromethoxy-1,1,2,2-tetrafluoroethyl (AF
9925/031.EST) difluoromethyl ether (HFPE2), to be used as substitutes of
CFC 113, consisting essentially of:
composition
% by weight
general preferred
I) difluoromethoxy 2-60 2-54
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1-dichloro-2,2,2-trifluoroethane 98-40 98-46
(CHCl.sub.2 CF.sub.3, HCFC 123)
II) difluoromethoxy 1-95 25-95
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
n-pentane 99-5 75-5
III) difluoromethoxy 1-99 25-98
bis(difluoromethyl ether)
(HFC.sub.2 OCF.sub.2 OCF.sub.2 H);
iso-pentane 99-1 75-2
IV) difluoromethoxy 1-60 20-60
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
dimethyl ketone (acetone) 99-40 80-40
V) difluoromethoxy 1-99 10-98
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,3,3-pentafluorobutane 99-1 90-2
(CF.sub.3 CH.sub.2 CF.sub.2 CH.sub.3, HFC 365 mfc)
VI) difluoromethoxy 1-40 10-40
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,4,4,4-hexafluorobutane 99-60 90-60
(CF.sub.3 CH.sub.2 CH.sub.2 CF.sub.3, HFC 356 ffa)
VII) difluorometoxy 1-96 25-96
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
methoxymethyl methylether 99-14 75-14
VIII) difluoromethoxy 30-99 35-98
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2);
n-hexane 70-1 65-2
IX) difluoromethoxy 1-99 18-95
bis(difluoromethyl ether)
(HCF.sub.2 OCF.sub.2 OCF.sub.2);
trans 1,2-dichloroethylene 99-1 82-5
(ClCHCHCl, tDCE)
X) 1-difluoromethoxy 1-93 25-93
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
n-pentane 99-7 75-7
XI) 1-difluoromethoxy 30-99 50-98
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
dimethyl ketone (acetone) 70-1 50-2
XII) 1-difluoromethoxy 50-99 60-98
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
methyl alcohol 50-1 40-2
XIII) 1-difluoromethoxy 15-99 25-98
1,1,2,2 -tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
n-hexane 85-1 75-2
XIV) 1-difluoromethoxy 1-99 15-95
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
trans 1,2-dichloroethylene 99-1 85-5
(ClCHCHCl)
XV) 1-difluoromethoxy 5-99 10-98
1,1,2,2-tetrafluoroethyl
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
ethyl alcohol 95-1 90-2
More specifically the azeotropic compositions, i.e. showing an absolute
minimum or maximum in the boiling temperature at the pressure of 1.013 bar
with respect to the pure products is noticed, are defined as follows:
Compositions
are defined within
+/- 2% by weight
A) difluoromethoxy-bis(difluoromethyl ether) 24% by wt.
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1-dichloro-2,2,2-trifluoroethane 76% by wt.
(CHCl.sub.2 CF.sub.3, HCFC 123)
B) difluoromethoxy-bis(difluoromethyl ether) 62% by wt.
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
n-pentane 38% by wt.
C) difluoromethoxy-bis(difluoromethyl ether) 63% by wt.
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
iso-pentane 36% by wt.
D) difluoromethoxy-bis(difluoromethyl ether) 42% by wt.
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
dimethyl ketone (acetone) 58% by wt.
E) difluoromethoxy-bis(difluoromethyl ether) 60% by wt.
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,3,3-pentafluorobutane 40% by wt.
(CF.sub.3 CH.sub.2 CF.sub.2 CH.sub.3, HFC 365 mfc)
F) difluoromethoxy-bis(difluoromethyl ether) 20% by wt.
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,4,4,4-hexafluorobutane 80% by wt.
(CF.sub.3 CH.sub.2 CH.sub.2 CF.sub.3, HFC 356 ffa)
C) difluoromethoxy-bis(difluoromethyl ether) 59% by wt.
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
methoxymethyl methyl ether 41% by wt.
H) difluoromethoxy-bis(difluoromethyl ether) 75% by wt.
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
n-hexane 25% by wt.
I) difluoromethoxy-bis(difluoromethyl ether) 75% by wt.
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
trans 1,2-dichloroethylene 25% by wt.
(ClCHCHCl, tDCE)
L) 1-difluoromethoxy-1,1,2,2-tetrafluoroethyl 61% by wt.
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
n-pentane 39% by wt.
M) 1-difluoromethoxy-1,1,2,2-tetrafluoroethyl 79% by wt.
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
dimethyl ketone (acetone) 21% by wt.
N) 1-difluoromethoxy-1,1,2,2-tetrafluoroethyl 94% by wt.
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
methyl alcohol 6% by wt.
Q) 1-difluoromethoxy-1,1,2,2-tetrafluoroethyl 74% by wt.
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
n-hexane 26% by wt.
P) 1-difluoromethoxy-1,1,2,2-tetrafluoroethyl 50% by wt.
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
trans 1,2-dichloroethylene 50% by wt.
(ClCHCHCl, tDCE)
Q) 1-difluoromethoxy-1,1,2,2-tetrafluoroethyl 95% by wt.
difluoromethyl ether
(HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H);
ethyl alcohol 5% by wt.
The azeotropic or near azeotropic mixtures, object of the present
invention, are based on two hydrofluoropolyethers: HFPE1 and HFPE2,
obtained by alkaline salt decarboxylation processes obtained by hydrolysis
and salification of the corresponding acylfluorides, using processes known
in the art. For example, decarboxylation is carried out in the presence of
hydrogen-donor compounds, for example water, at temperatures of
140-170.degree. C. and under a pressure of at least 4 atm. See for example
EP 695,775 and the examples reported therein; this patent is herein
incorporated by reference.
The main features of the two hydrofluoropolyethers of the azeotropic or
near azeotropic mixtures, are reported in Table 1 in comparison with CFC
113.
The fluids in Table I are characterized by a combination of
chemical-physical properties such as chemical inertia, high thermal
stability, non flammability, evaporation heat and boiling temperature such
as to be particularly suitable, in admixture with other organic solvents
as defined above, for the CFC 113 substitution in the above mentioned
industrial applications.
Preliminary studies relating to acute toxicity show that the products have
a low biologic activity.
The Applicant has found that the particular distribution of the hydrogen
atoms on the terminal ends and the presence of an ethereal bond prevents
dehydrofluorination reactions, which lead to the formation of potentially
toxic olefins and avoids the acidity formation which involves metal
material corrosion phenomena.
The HFPEs of the invention have an ODP value equal to zero and a low GWP.
The HFPE-based mixtures offer an advantageous combination of the boiling
temperature and evaporation heat such as to give them a detergency/drying
time suitably short and fit to the continuous operations, both in liquid
and in vapour phase.
The evaporation heat is sufficiently low and such as not to allow the
solidification of the water trace which must be removed.
In the detergency, solvency and drying applications, the use of mixtures
having an azeotropic or near azeotropic behaviour is essential, in order
to avoid segregations or meaningful variations of the fluid composition
during the industrial processes phases involving phase change phenomena
(evaporation and condensation), as in the solvency case, and, more
generally, during all the fluid handling and storage operations in which
accidental leaks can take place due to liquid evaporation and consequently
variations of the composition of the fluid.
The composition variations which take place in all the cases wherein non
azeotropic mixtures are used, involve deviations of the solvent agent
performances and the need to make appropriated refillings in order to
restore the original composition and therefore the mixture
chemical-physical characteristics.
Furthermore, when the non azeotropic or non near-azeotropic compositions
contain more volatile flammable components, the vapour phase becomes rich
in such component until reaching the flammability limit, with evident
risks for the use safety. Likewise, when the flammable component is less
volatile, it concentrates in the liquid phase giving rise to a flammable
liquid.
Mixtures having azeotropic or near azeotropic behaviour avoid the above
disadvantage even when a flammable compound is present
An azeotrope is a particular composition which has singular
chemical-physical, unexpected and unforeseeable properties of which the
most important ones are reported hereinafter.
An azeotrope is a mixture of two or more fluids which has the same
composition in the vapour phase and in the liquid one when it is in
equilibrium under determined conditions.
The azeotropic composition is defined by particular temperature and
pressure values; in these conditions the mixtures undergo phase changes at
constant composition and temperature as pure compounds.
A near azeotrope is a mixture of two or more fluids which has a vapour
composition substantially equal to that of the liquid and undergo phase
passages without substantially modifying the composition and temperature.
A composition is near azeotropic when, after evaporation at a constant
temperature of 50% of the liquid initial mass, the per cent variation of
the vapour pressure between the initial and final composition results
lower than 10%; in the case of an azeotrope, no variation of the vapour
pressure between the initial composition and the one obtained after the
50% liquid evaporation is noticed.
Azeotropic or near azeotropic mixtures belong to the cases showing
meaningful, both positive and negative, deviations from the Raoult law. As
known to the skilled in the art, such law is valid for ideal systems.
When such deviations are sufficiently marked, the mixture vapour pressure
in the azeotropic point must be therefore characterized by values either
higher or lower than those of the pure compounds.
It is evident that, if the mixture vapour pressure curve shows a maximum,
this corresponds to a minimum of boiling temperature; viceversa to a
vapour pressure minimum value, a maximum of boiling temperature
corresponds.
The azeotropic mixture has only one composition for each temperature and
pressure value.
However, by changing temperature and pressure, more azeotropic compositions
starting from the same components can be obtained.
For example, the combination of all the compositions of the same components
which have a minimum or a maximum in the boiling temperature at different
pressure levels form an azeotropic composition field.
It has been found that the near azeotropic compositions of points I, III,
IV, V, VI, VII remain near azeotropic also when a portion of
difluoromethoxy-bis(difluoromethyl ether) is substituted with
1-difluoromethoxy-1,1,2,2-tetrafluoroethyldifluoromethyl ether up to 40%
by weight.
The same for compositions of points XI, XII and XV when a portion of
1-difluoromethoxy-1,1-2,2-tetrafluoroethyl difluoromethyl ether is
substituted by difluoromethoxy-bis(difluoromethyl ether), up to 40% by
weight.
The same for compositions of points II, VIII and IX wherein a part of
difluoromethoxy-bis(difluoromethyl ether) is replaced by
1-difluoromethoxy-1,1,2,2-tetrafluoroethyldifluoromethyl ether up to 50%
by weight.
Likewise for the compositions of points X, XIII and XIV wherein a portion
of 1-difluoromethoxy-1,1,2,2-tetrafluoroethyl difluoromethyl ether is
replaced by difluoromethoxy-bis(difluoromethyl ether) up to 50% by weight.
Another object of the present invention are ternary near azeotropic
compositions based on difluoromethoxy-bis(difluoromethyl ether) and
hydrocarbons consisting essentially of:
% by weight
XVI) difluoromethoxy-bis(difluoromethyl ether) 1-42
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1-dichoro-2,2,2-trifluoroethane 98-24
(CHCl.sub.2 CF.sub.3, HCFC 123)
hydrocarbon 1-35
XVII) difluoromethoxy-bis(difluoromethyl ether) 1-64
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,3,3-pentafluorobutane 98-1
(CF.sub.3 CH.sub.2 CF.sub.2 CH.sub.3, HFC 365 mfc)
hydrocarbon 1-35
XVIII) difluoromethoxy-bis(difluoromethyl ether) 1-22
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,4,4,4-hexafluorobutane 98-43
(CF.sub.3 CH.sub.2 CH.sub.2 CF.sub.3, HFC 356 ffa)
hydrocarbon 1-35
Among hydrocarbons, n-pentane and iso-pentane are preferred, preferably in
the range 1-20% by weight.
Likewise, an object of the present invention are ternary near azeotropic
compositions based on difluoromethoxy-bis(difluoromethyl ether) and
alcohols essentially consisting of:
% by weight
XIX) difluoromethoxy-bis(difluoromethyl ether) 1-55
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H)
1,1-dichloro-2,2,2-trifluoroethane 98-35
(CHCl.sub.2 CF.sub.3, HCFC 123)
alcohol 1-10
XX) difluoromethoxy-bis(difluoromethyl ether) 1-89
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,3,3-pentafluorobutane 98-1
(CF.sub.3 CH.sub.2 CF.sub.2 CH.sub.3, HFC 365 mfc)
alcohol 1-10
XXI) difluoromethoxy-bis(difluoromethyl ether) 1-35
(HCF.sub.2 OCF.sub.2 OCF.sub.2 H);
1,1,1,4,4,4-hexafluorobutane 98-55
(CF.sub.3 CH.sub.2 CH.sub.2 CF.sub.3, HFC 356 ffa)
alcohol 1-10
Preferred alcohol is methyl alcohol; preferably between 1 and 5% by weight.
A further object of the present invention are azeotropic or near azeotropic
compositions, as described at points from I) to XXI) and from A) to Q),
wherein, a portion of HFPE1 and/or HFPE2 is replaced by a
hydrofluoropolyethers having the same structure of HFPE1 or HFPE2 but
having boiling point in the range of 5-80.degree. C. In this case, one can
speak of fluids consisting essentially of HFPE1 and/or HFPE2.
In the detergency applications the mentioned mixtures can be used in
combination with stabilizing agents in order to limit the radicalic
decomposition reactions which, as known, are favoured by the temperature
and the metal presence. The degradation reactions especially concerning
the mixtures containing HCFC 123, HFC 356 ffa and 365 mfc, can always be
prevented or reduced by the use of nitroparaffins and/or organic
substances in the molecule of which conjugated double bonds are present.
The stabilizing agents are generally used in amounts of 0.1-5% by weight.
To the compositions of the invention, non ionic surfactant agents soluble
therein can be added to decrease the interfacial tension with water and
favour the water removal from the surfaces subjected to drying. The used
surfactant concentration is in the range 0.005%-5% by weight on the
azeotropic or near azeotropic components, i.e. on the solvent/drying
agent.
The compositions of the present invention can be used also in aerosol
applications for the electronic components cleaning in combination with
one or more propellants, preferably selected from HFC 134a
(1,1,1,2-tetrafluoroethane), HFC 227ea (1,1,1,2,3,3,3-heptafluoropropane)
or mixtures thereof.
EXAMPLE 1
The evaluation of the azeotropic or near azeotropic behaviour is made as
follows: the mixture of known composition and weight is introduced in a
small glass cell, previously evacuated, having an internal volume equal to
about 20 cm.sup.3, equipped with metal connections, feeding valve and a
pressure transducer to evaluate the system vapour pressure.
The filling volumetric ratio is initially equal to about 0.8%v.
The cell is introduced in a thermostatic bath and the temperature is slowly
changed until obtaining a vapour pressure equilibrium value equal to 1.013
bar. The corresponding temperature is recorded and it represents the
mixture boiling temperature at the 1.013 bar pressure.
The temperature is measured close to the equilibrium cell with a
thermometer the accuracy of which is equal to .+-.0.01.degree. C.;
particular attention was paid so that the external temperature measured in
the bath is really the internal one of the cell.
By changing the mixture composition it is possible to estimate possible
deviations with respect to the ideality and therefore to identify the
azeotropic composition which, as said, will be characterized by an
absolute minimum or maximum with respect to the pure components.
In order to confirm the azeotropic or near azeotropic behaviour, the
mixture characterized by a minumum or a maximum of the boiling temperature
and others identified close to the azeotrope were subjected to evaporation
test at the azeotrope constant temperature.
The cell content is removed at constant temperature by evaporation until
having a loss corresponding to 50% by weight of the initial amount.
From the evaluation of the initial and final pressure the per cent
variation of the vapour pressure is calculated: if the decrease is equal
to zero the mixture in those conditions is an azeotrope, if the decrease
is <10% its behaviour is of a near azotrope.
It is known that a near azetropic mixture has a behaviour closer and closer
to a true azeotrope if the per cent variation is lower and lower and near
to zero.
As a further confirmation of the azeotropic and near azeotropic behaviour,
togheter with the above reported evaluations, analyses of the composition
of some mixtures object of the present invention, have been carried out by
gaschromatographic method before and after the evaporation test.
The azeotropic mixtures maintain unchanged, within the limits of the error
of the analytical methods, the composition after the liquid evaporation,
while in the case of near azeotropic systems, limited variations of
composition are observed.
In all the measurements reported in Tables from 2 to 18 the visual
observation of the liquid phase at its normal boiling temperature has in
any case shown that no phase separations took place and that the solutions
were limpid and homogeneous.
TABLE 1
Hydrofluoropolyether chemical-physical and
toxicological characteristics
CFC 113
1,1,2-tri-
chloro
1,2,2-tri-
Chemical HCF.sub.2 OCF.sub.2 OCF.sub.2 H HCF.sub.2 OCF.sub.2 CF.sub.2
OCF.sub.2 H fluro-
structure (HFPE1) (HFPE2) roethane
Molecular mass 184.04 234.05 187.38
Boiling 35.39 58.21 47.55
temperature
(.degree. C.,
at 1.013 bar)
Evaporation 165 139 144
latent
heat
(KJ/Kg,
at 1.013 bar)
Liquid density 1.54 1.60 1.56
at 25.degree. C.
(g/cm.sup.3)
Flammability non flammable non flammable non
in air flammable
(% volume)
ODP CFC 0 0 1.07
11 = 1
lifetime <10 <10 110
(years)
Acute toxicity >5000 >5000 43000
in rats per os,
LD.sub.50
(ppmv/4 hours)
Acute toxicity >32000 >32000 50000
in rats by
inhalation,
LC.sub.50
(ppmv/4 hours)
Surface 14.0 15.5 18.1
pressure at
20.degree. C.
(dynes/cm)
Isotherm 1.5 0.6 1
evaporation
speed at 20.degree. C.
(mg/min)
TABLE No 2
boiling temperature evaluation at the pressure
of 1.013 bar
HCF.sub.2 OCF.sub.2 OCF.sub.2 H/HCFC 123 binary mixture
COMPOSITION BOILING TEMPERATURE
HCF.sub.2 OCF.sub.2 OCF.sub.2 H (% by wt.) (.degree. C.)
0 27.54
5.4 27.00
7.7 26.77
13.0 26.75
16.3 26.71
20.1 26.70
24.2 26.68
26.1 26.71
40.0 26.96
49.3 27.21
60.2 27.86
72.6 29.39
100 35.39
TABLE No 2
boiling temperature evaluation at the pressure
of 1.013 bar
HCF.sub.2 OCF.sub.2 OCF.sub.2 H/HCFC 123 binary mixture
COMPOSITION BOILING TEMPERATURE
HCF.sub.2 OCF.sub.2 OCF.sub.2 H (% by wt.) (.degree. C.)
0 27.54
5.4 27.00
7.7 26.77
13.0 26.75
16.3 26.71
20.1 26.70
24.2 26.68
26.1 26.71
40.0 26.96
49.3 27.21
60.2 27.86
72.6 29.39
100 35.39
TABLE 3
boiling temperature evaluation at the pressure of
1.013 bar
HCF.sub.2 OCF.sub.2 OCF.sub.2 H/n-pentane binary mixture
COMPOSITION BOILING TEMPERATURE
HCF.sub.2 OCF.sub.2 OCF.sub.2 H (% by weight) (.degree. C.)
0 35.79
12.6 26.42
25.9 23.00
50.0 21.45
61.9 21.32
74.9 21.35
83.4 21.49
87.0 21.70
95.6 25.18
100 35.39
TABLE 3
boiling temperature evaluation at the pressure of
1.013 bar
HCF.sub.2 OCF.sub.2 OCF.sub.2 H/n-pentane binary mixture
COMPOSITION BOILING TEMPERATURE
HCF.sub.2 OCF.sub.2 OCF.sub.2 H (% by weight) (.degree. C.)
0 35.79
12.6 26.42
25.9 23.00
50.0 21.45
61.9 21.32
74.9 21.35
83.4 21.49
87.0 21.70
95.6 25.18
100 35.39
TABLE 4
evaluation of the boiling temperature at the
pressure of 1.013 bar
HCF.sub.2 OCF.sub.2 OCF.sub.2 H/iso-pentane binary mixture
COMPOSITION BOILING TEMPERATURE
HCF.sub.2 OCF.sub.2 OCF.sub.2 H (% by wt.) (.degree. C.)
0 27.18
14.2 21.02
20.4 20.00
39.5 17.70
61.0 17.40
63.1 17.35
80.1 17.68
90.4 19.80
100 35.39
TABLE 4
evaluation of the boiling temperature at the
pressure of 1.013 bar
HCF.sub.2 OCF.sub.2 OCF.sub.2 H/iso-pentane binary mixture
COMPOSITION BOILING TEMPERATURE
HCF.sub.2 OCF.sub.2 OCF.sub.2 H (% by wt.) (.degree. C.)
0 27.18
14.2 21.02
20.4 20.00
39.5 17.70
61.0 17.40
63.1 17.35
80.1 17.68
90.4 19.80
100 35.39
TABLE 5
evaluation of the boiling temperature at the
pressure of 1.013 bar
HCF.sub.2 OCF.sub.2 OCF.sub.2 H/acetone binary mixture
COMPOSITION
HCF.sub.2 OCF.sub.2 OCF.sub.2 H BOILING TEMPERATURE
(% by wt.) (.degree. C.)
0 56.50
28.1 57.88
41.7 58.11
51.0 57.98
61.2 56.63
74.8 53.62
100 35.39
TABLE 5
evaluation of the boiling temperature at the
pressure of 1.013 bar
HCF.sub.2 OCF.sub.2 OCF.sub.2 H/acetone binary mixture
COMPOSITION
HCF.sub.2 OCF.sub.2 OCF.sub.2 H BOILING TEMPERATURE
(% by wt.) (.degree. C.)
0 56.50
28.1 57.88
41.7 58.11
51.0 57.98
61.2 56.63
74.8 53.62
100 35.39
TABLE 6
evaluation of the boiling temperature at the
pressure of 1.013 bar
HCF.sub.2 OCF.sub.2 OCF.sub.2 H/HFC 365 mfc binary mixture
COMPOSITION BOILING TEMPERATURE
HCF.sub.2 OCF.sub.2 OCF.sub.2 H (% by wt.) (.degree. C.)
0 40.09
10.0 36.89
20.0 34.92
30.0 33.71
40.1 33.01
50.1 32.66
60.1 32.60
75.0 33.13
80.0 33.54
100 35.39
TABLE 6
evaluation of the boiling temperature at the
pressure of 1.013 bar
HCF.sub.2 OCF.sub.2 OCF.sub.2 H/HFC 365 mfc binary mixture
COMPOSITION BOILING TEMPERATURE
HCF.sub.2 OCF.sub.2 OCF.sub.2 H (% by wt.) (.degree. C.)
0 40.09
10.0 36.89
20.0 34.92
30.0 33.71
40.1 33.01
50.1 32.66
60.1 32.60
75.0 33.13
80.0 33.54
100 35.39
TABLE 7
evaluation of the boiling temperature at the
pressure of 1.013 bar
HCF.sub.2 OCF.sub.2 OCF.sub.2 H/HFC 356 ffa binary mixture
COMPOSITION BOILING TEMPERATURE
HCF.sub.2 OCF.sub.2 OCF.sub.2 H (% by wt.) (.degree. C.)
0 24.71
10.1 24.16
19.9 24.05
29.9 24.22
40.0 24.65
49.9 25.29
60.1 26.24
70.1 27.60
80.1 29.65
100 35.39
TABLE 7
evaluation of the boiling temperature at the
pressure of 1.013 bar
HCF.sub.2 OCF.sub.2 OCF.sub.2 H/HFC 356 ffa binary mixture
COMPOSITION BOILING TEMPERATURE
HCF.sub.2 OCF.sub.2 OCF.sub.2 H (% by wt.) (.degree. C.)
0 24.71
10.1 24.16
19.9 24.05
29.9 24.22
40.0 24.65
49.9 25.29
60.1 26.24
70.1 27.60
80.1 29.65
100 35.39
TABLE 8
evaluation of the boiling temperature at the
pressure of 1.013 bar
HCF.sub.2 OCF.sub.2 OCF.sub.2 H/metoxymethyl methyl ether binary mixture
COMPOSITION
HCF.sub.2 OCF.sub.2 OCF.sub.2 H (% by wt.) BOILING TEMPERATURE,
.degree. C.
0 41.96
20.1 42.80
27.5 43.05
38.1 43.40
50.6 43.78
59.1 43.74
60.2 43.76
65.0 43.53
72.1 42.95
78.7 41.66
100 35.39
TABLE 8
evaluation of the boiling temperature at the
pressure of 1.013 bar
HCF.sub.2 OCF.sub.2 OCF.sub.2 H/metoxymethyl methyl ether binary mixture
COMPOSITION
HCF.sub.2 OCF.sub.2 OCF.sub.2 H (% by wt.) BOILING TEMPERATURE,
.degree. C.
0 41.96
20.1 42.80
27.5 43.05
38.1 43.40
50.6 43.78
59.1 43.74
60.2 43.76
65.0 43.53
72.1 42.95
78.7 41.66
100 35.39
TABLE 9
evaluation of the boiling temperature at the
pressure of 1.013 bar
HCF.sub.2 OCF.sub.2 OCF.sub.2 H/n-hexane binary mixture
COMPOSITION BOILING TEMPERATURE
HCF.sub.2 OCF.sub.2 OCF.sub.2 H (% by wt.) (.degree. C.)
0 68.00
15.4 43.86
34.0 35.15
50.8 33.12
65.6 32.42
74.7 32.10
78.1 32.15
90.1 32.22
100 35.39
TABLE 9
evaluation of the boiling temperature at the
pressure of 1.013 bar
HCF.sub.2 OCF.sub.2 OCF.sub.2 H/n-hexane binary mixture
COMPOSITION BOILING TEMPERATURE
HCF.sub.2 OCF.sub.2 OCF.sub.2 H (% by wt.) (.degree. C.)
0 68.00
15.4 43.86
34.0 35.15
50.8 33.12
65.6 32.42
74.7 32.10
78.1 32.15
90.1 32.22
100 35.39
TABLE 10
evaluation of the boiling temperature at the
pressure of 1.013 bar
HCF.sub.2 OCF.sub.2 OCF.sub.2 H/ tDCE binary mixture
COMPOSITION BOILING TEMPERATURE
HCF.sub.2 OCF.sub.2 OCF.sub.2 H (% by wt.) (.degree. C.)
0 46.70
6.0 40.65
6.7 40.05
24.2 33.02
40.5 30.96
59.1 29.85
70.2 29.79
75.1 29.76
84.8 30.13
94.2 31.88
100 35.39
TABLE 10
evaluation of the boiling temperature at the
pressure of 1.013 bar
HCF.sub.2 OCF.sub.2 OCF.sub.2 H/ tDCE binary mixture
COMPOSITION BOILING TEMPERATURE
HCF.sub.2 OCF.sub.2 OCF.sub.2 H (% by wt.) (.degree. C.)
0 46.70
6.0 40.65
6.7 40.05
24.2 33.02
40.5 30.96
59.1 29.85
70.2 29.79
75.1 29.76
84.8 30.13
94.2 31.88
100 35.39
TABLE 11
evaluation of the boling temperature at the
pressure of 1.013 bar
HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H/n-pentane binary mixture
COMPOSITION BOILING TEMPERATURE
HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H (% by wt.) (.degree. C.)
0 35.79
17.3 31.75
29.1 31.52
60.8 31.2
68.0 31.04
72.1 31.08
74.3 31.15
79.3 31.25
84.3 31.77
93.4 35.83
100 58.21
TABLE 11
evaluation of the boling temperature at the
pressure of 1.013 bar
HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H/n-pentane binary mixture
COMPOSITION BOILING TEMPERATURE
HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H (% by wt.) (.degree. C.)
0 35.79
17.3 31.75
29.1 31.52
60.8 31.2
68.0 31.04
72.1 31.08
74.3 31.15
79.3 31.25
84.3 31.77
93.4 35.83
100 58.21
TABLE 12
boiling temperature evaluation at the pressure of
1.013 bar
HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H/acetone binary mixture
COMPOSITION BOILING TEMPERATURE
HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H (% by wt.) (.degree. C.)
0 56.50
15.5 56.83
30.8 58.23
40.7 59.45
58.6 62.87
70.0 65.04
79.4 65.96
85.5 65.28
89.9 64.41
100 58.21
TABLE 12
boiling temperature evaluation at the pressure of
1.013 bar
HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H/acetone binary mixture
COMPOSITION BOILING TEMPERATURE
HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H (% by wt.) (.degree. C.)
0 56.50
15.5 56.83
30.8 58.23
40.7 59.45
58.6 62.87
70.0 65.04
79.4 65.96
85.5 65.28
89.9 64.41
100 58.21
TABLE 13
evaluation of the boiling temperature at the
pressure of 1.013 bar
HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H/methyl alcohol binary mixture
COMPOSITION BOILING TEMPERATURE
HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H (% by wt.) (.degree. C.)
0 65.00
21.0 63.15
40.3 59.95
50.0 57.88
73.8 53.45
84.3 52.18
88.7 51.83
93.9 51.38
96.5 53.87
100 58.21
TABLE 13
evaluation of the boiling temperature at the
pressure of 1.013 bar
HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H/methyl alcohol binary mixture
COMPOSITION BOILING TEMPERATURE
HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H (% by wt.) (.degree. C.)
0 65.00
21.0 63.15
40.3 59.95
50.0 57.88
73.8 53.45
84.3 52.18
88.7 51.83
93.9 51.38
96.5 53.87
100 58.21
TABLE 14
boiling temperature evaluation at the pressure of
1.013 bar
HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H/n-hexane binary mixture
COMPOSITION BOILING TEMPERATURE
HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H (% by wt.) (.degree. C.)
0 68.00
20.6 56.24
39.7 48 81
59.9 46.74
73.8 46.66
78.7 46.76
89.9 49.00
100 58.21
TABLE 14
boiling temperature evaluation at the pressure of
1.013 bar
HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H/n-hexane binary mixture
COMPOSITION BOILING TEMPERATURE
HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H (% by wt.) (.degree. C.)
0 68.00
20.6 56.24
39.7 48 81
59.9 46.74
73.8 46.66
78.7 46.76
89.9 49.00
100 58.21
TABLE 15
boiling temperature evaluation at the pressure of
1.013 bar
HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H/tDCE binary mixture
COMPOSITION BOILING TEMPERATURE
HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H (% by wt.) (.degree. C.)
0 46.79
5.6 44.16
20.5 41.28
35.2 40.43
45.1 40.22
50.0 40.17
54.7 40.18
64.9 40.26
75.5 40.99
86.0 43.22
95.0 49.37
100 58.21
TABLE 15
boiling temperature evaluation at the pressure of
1.013 bar
HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H/tDCE binary mixture
COMPOSITION BOILING TEMPERATURE
HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H (% by wt.) (.degree. C.)
0 46.79
5.6 44.16
20.5 41.28
35.2 40.43
45.1 40.22
50.0 40.17
54.7 40.18
64.9 40.26
75.5 40.99
86.0 43.22
95.0 49.37
100 58.21
TABLE 16
boiling temperature evaluation at the pressure of
1.013 bar
HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H/ethyl alcohol binary mixture
COMPOSITION BOILING TEMPERATURE
HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H (% by wt.) (.degree. C.)
0 78.50
20.6 72.35
48.9 63.70
62.6 60.12
80.0 57.33
89.7 56.07
94.7 55.65
98.0 55.75
99.0 56.02
100 58.21
TABLE 16
boiling temperature evaluation at the pressure of
1.013 bar
HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H/ethyl alcohol binary mixture
COMPOSITION BOILING TEMPERATURE
HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H (% by wt.) (.degree. C.)
0 78.50
20.6 72.35
48.9 63.70
62.6 60.12
80.0 57.33
89.7 56.07
94.7 55.65
98.0 55.75
99.0 56.02
100 58.21
TABLE 17
Azeotropic and near azeotropic behaviour
evaluation by determination of the vapour pressure per cent
variation after evaporation of 50% of the initial liquid
mass
Binary mixtures of difluoromethoxy-bis (difluoromethyl e-
ther)/1-difluoromethoxy-1,1,2,2-tetrafluoroethyl di-
fluoromethyl ether
Initial composi-
tion
HCF.sub.2 OCF.sub.2 OCF.sub.2 H/
HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H Temperature Initial pressure
.DELTA.P/P .times. 100
(% by wt.) (.degree. C.) (bar) (%)
50.0/50.0 43.00 1.013 9.28
11.8/83.9* 53.97 1.013 6.71
60.3/39.7 41.57 1.013 5.92
*contains 4.3% by weight of heavier impurities formed by HFPE having a
higher molecular weight
TABLE 17
Azeotropic and near azeotropic behaviour
evaluation by determination of the vapour pressure per cent
variation after evaporation of 50% of the initial liquid
mass
Binary mixtures of difluoromethoxy-bis (difluoromethyl e-
ther)/1-difluoromethoxy-1,1,2,2-tetrafluoroethyl di-
fluoromethyl ether
Initial composi-
tion
HCF.sub.2 OCF.sub.2 OCF.sub.2 H/
HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H Temperature Initial pressure
.DELTA.P/P .times. 100
(% by wt.) (.degree. C.) (bar) (%)
50.0/50.0 43.00 1.013 9.28
11.8/83.9* 53.97 1.013 6.71
60.3/39.7 41.57 1.013 5.92
*contains 4.3% by weight of heavier impurities formed by HFPE having a
higher molecular weight
EXAMPLE 2
The solvent effect of the HFPE-based mixtures is evaluated by determination
of the Kauri-butanol index, reported in Table 19, according to ASTM
D1133-86 method. The test has been however modified to limit the losses
due to the solvent evaporation with boiling temperature lower than
40.degree. C.; a 100 ml flask is used as vessel for the Kauri-butanol
solution; the end part of the buret containing the solvent is inserted in
a holed stopper closing the flask so as to carry out the titration
limiting the solvent evaporation. The Kauri-butanol solution is stirred by
a magnetic stirrer. The end titration point is identified in connection
with a diffused turbidity which appears in the Kauri-butanol solution due
to the resin separation.
TABLE 19
Composition
Solvent (% by wt.) Kauri-butanol index
CFC 113 (comp) 100 31
HFPE1/HFPE2/HCFC 123 14.5/9.5/76.0 33
Example composition I
HFPE1/HFPE2/n-pentane 12.0/49.0/39.0 25
Example compositions II, X
HFPE1/HFPE2/n-hexane 14.8/59.0/26.2 26
Example compositions VII,
XIII
HFPE1/HFPE2/tDCE 6.2/43.8/50.0 24
Example compositions IX, XIV
HFPE1 = HCF.sub.2 OCF.sub.2 OCF.sub.2 H
HFPE2 = HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H
EXAMPLE 3
The oily product removal capacity from molded circuits has been verified
according to the following method: a known amount of an oily product is
uniformly spread on the molded circuit surface having 35.times.19 mm
sizes; 0.100 g of oil are spread on a single surface of the circuit, then
the article is dipped in the solution to be tested.
After 5 minutes of dipping, the circuit is allowed to drie for further 5
minutes at room temperature so as to remove the solvent traces and then it
is weighed again on an analytical balance.
The following oily products have been used:
1) Alkyl Benzene-Zerice S 46 oil by ESSO
2) FluoroSilicone-FS 1265 oil by DOW CORNIG
3) Ester-Icematic SW 100 oil by CASTROL
4) Mineral-Clavus 32 oil by SHELL.
Tests are carried out at room temperature (23-250.degree. C.) and tests at
the boiling temperature of the solvent mixtures. In the latter case the
solvent is placed in a vessel equipped with a refrigerant under reflux
which recovers the vapour of the boiling solution.
In all the tests 30 ml of solvent solution have been used.
The results are reported in Table 20 expressed as removed oil percentage.
TABLE 20
Percentage of removed oil for
Temperature type of oil (% by weight)
SOLVENT .degree. C. (1) (2) (3) (4)
CFC 113 (comp) 23 100 99.5 100 100
# .rect-ver-solid. # #
HFPE1/HFPE2/HCFC123 23 100 100 100 100
(14.5)(9.5)(76.0) # # # #
Example composition I
HFPE1/HFPE2/n-pentane 23 100 100 100 100
(12.0)(49.0)(39.0) # # # #
Example compositions
II, X
HFPE1/HFPE2/n-esano 23 100 100 100 100
(14.8)(59.0)(26.2) # # # #
Example compositions
VII, XIII
HFPE1/HFPE2/methyl 51 88.1 100 100 81.0
alcohol .rect-ver-solid. # #
.rect-ver-solid.
(18.8)(75.1)(6.1)
Example composition
XII
HFPE1/HFPE2/tDCE 25 100 100 100 100
(6.2)(43.8)(50.0) # # # #
Example compositions
IX, XIV
HFPE1/HFPE2/acetone 66 100 100 100 100
(15.9)(63.5)(20.6) .rect-ver-solid. # #
.rect-ver-solid.
Example compositions
IV, XI
HFPE1 = HCF.sub.2 OCF.sub.2 OCF.sub.2 H
HFPE2 = HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H
1) Alkyl Benzene-Zerice S 46 oil by ESSO
2) FluoroSilicone-FS 1265 oil by DOW CORNIG
3) Ester-Icematic SW 100 oil by CASTROL
4) Mineral-Clavus 32 oil by SHELL.
.rect-ver-solid. The removed oil is not completely soluble in the solvent
mixture at the test temperature
# the oil removed is completely soluble in the solvent mixture at the test
temperature.
In many cases with the mixtures reported in Table 20 it is possible to
obtain a wide solvent action towards oily products of different type with
results higher than or comparable with those offered by CFC 113.
Furthermore, the great availability of azeotropic and near azeotropic
mixtures allows to select the best composition in connection with the type
of oily substance to be removed.
EXAMPLE 4
The HFC 134a and HFC 227 ea solubility with some solvent compositions for
aerosol applications for the cleaning of electronic components is reported
hereinafter.
TABLE 21
Propellant con-
centration in
admixture with
Solvent com- the solvent Temperature
positions compositions (.degree. C.)
(% by wt.) Propellant (% by weight) 0 25 50
HFPE1/HFPE2/ HFC 134a 49.2 S S S
n-hexane
(14.8) (59.0)
(26.2)
HFPE1/HFPE2/ HFC 134a 48.8 S S S
acetone
(15.9) (63.5)
(20.6)
HFPE1/HFPE2/- HFC 134a 50.7 S S S
methoxymethyl
methylether
(35.0) (24.0)
(41.0)
HFPE1/HFPE2/- HFC 227ea 38.1 S S S
methoxymethyl
methylether
(35.0) (24.0)
(41.0)
HFPE1 = HCF.sub.2 OCF.sub.2 OCF.sub.2 H
HFPE2 = HCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 H
S = The propellant is completely soluble in the used solvent.
EXAMPLE 5
The water removal from glass surfaces by means of some compositions object
of the present invention is described.
In a cylindrical container having a 46 cm diameter and a 56 cm height,
equipped with a neoprene closing stopper (cover), 30 ml of the solution to
be tested are introduced.
The compositions, indicated in Table 22, used for the water removal tests
are prepared in a 50 ml flask and are heated in a thermostatic bath at a
temperature of about 5.degree. C. lower than the boiling temperature of
the solution itself.
The solutions are added of 600 ppm weight of a surfactant able to reduce
the interfacial tension with water and favour the removal phenomenon of
this from the surface subjected to drying; the tests have been carried out
in comparison with CFC 113 equivalently additioned of a surfactant
constituted by 1,1,2-dodecandiammonium-bis[di(3,6
dioxapentadecyl)phosphate].
After heating the solution is transferred in the test container equipped
with cover.
On a glass surface having 37.times.25.times.1 mm sizes, 0.015 g of water
are deposited in the form of small drops.
The glass is placed on a metal frame which is used to carry out the article
dipping in the liquid phase of the solution to be tested.
The container for the test is opened and the frame is slowly dipped into
the solution; the frame upper part runs in a hole made in the rubber cover
(cap) which closes the container.
When two minutes have elapsed, the frame is lifted from the liquid phase,
by letting run the external end part through the hole present in the cover
(cap); the glass will remain exposed to the solution vapours for one
minute, then it is removed from the container and weighed.
In Table 22 the results relating to the water removal tests in comparison
with the reference system formed by CFC 113, are reported.
The tested solutions allow to remove water in a similar way to the
reference system.
TABLE 22
AGENT Temperature removed water
solvent/drying (.degree. C.) (% by weight)
CFC 113* 42 100
HFPE1/HFPE2/HCFC123 23 100
(14.5) (9.5) (76.0))*
HFPE1/HFPE2/tDCE 35 100
(6.2) (43.8) (50.0)*
*contains 600 ppm by weight of 1,1,2-dodecandiammonium bis [di-(3,6
dioxapentadecyl)phosphate]
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